Jp. Guthrie et Ja. Barker, ALDOL CONDENSATION OF TRIFLUOROACETOPHENONE AND ACETONE - TESTING A PREDICTION, Journal of the American Chemical Society, 120(27), 1998, pp. 6698-6703
Rate and equilibrium constants have been determined for both stages of
the aldol condensation of acetone with trifluoroacetophenone. The ext
ensive hydration of trifluoroacetophenone and the acid dissociation of
the hydrate complicated the kinetic analysis. Dehydration of the inte
rmediate ketol leads to two enones which equilibrate in base more rapi
dly than they undergo hydration to the ketol. This is consistent with
interconversion via the enolate of the ketol, which loses OH- faster t
han it undergoes C-protonation. The rate constant determined for the a
ldol addition step is in satisfactory agreement with the value predict
ed from a Marcus correlation.